CN104934573A - In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof - Google Patents
In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof Download PDFInfo
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Abstract
The invention brings forward a novel low-cost in-situ solid-phase preparation method. By the method, a silicon-graphene spheroidal composite material with a multilevel structure can be synthesized by one step. The composite material can be used as a high specific energy anode material to be applied in a lithium ion battery. Low-cost organic carbohydrate and inorganic transition metal salt which are respectively used as a carbon source and a metal catalyst precursor are selected to be uniformly mixed with a silicon nano-material; by a tube furnace heating method, in-situ catalytic growth of a graphene coated network happens on the surface of silicon nano-particles; and through the bridging effect of the graphene network, spheroidal micro-scale particles with a nanometer fine structure is self-assembled. The silicon-graphene spheroidal composite anode material with the multilevel structure has an advantage of high specific capacity. In addition, two main bottleneck problems such as poor electronic conductivity of a silicon anode material and severe volume effect during the cyclic process can be overcome simultaneously, and multiplying power and cycle performance of silicon anode can be raised greatly.
Description
Technical field
The invention belongs to new energy materials and electrochemical energy source research field, be specifically related to a kind of original position synthesis in solid state with the spherical composite material of silicon-Graphene of multilevel hierarchy and the method applied in the full battery of lithium ion as height ratio capacity negative material thereof.
Background technology
Lithium ion battery, because of the high advantage of its energy density, obtains development at a high speed, and is widely used as the power supply of the portable type electronic products such as mobile phone, camera, notebook computer in the past 20 years.In recent years, the development of hybrid-electric car, plug-in hybrid-electric car and large-scale energy storage device, has higher requirement in energy density, high rate performance and cycle life to lithium ion battery of future generation.The theoretical capacity of graphite cathode material general at present only has 372 mAh g
-1, therefore improve negative material capacity and be considered to develop one of advanced battery system approach the most effective and important.The relative graphite material of height ratio capacity negative material, not only can significantly reduce its consumption, make battery lightening; When with height ratio capacity positive pole Proper Match, the qualitative change formula that also can realize lithium ion battery energy density improves.Up to the present, various types of materials comprises lithium alloy (Si, Sn, Ge, Sb), transition metal oxide (SnO
2, TiO
2, MnO
2, Co
3o
4, Fe
2o
3), transition metal nitride, high molecular polymer and corresponding composite material, be obtained for detailed research.Silicon as the highest material of wherein theoretical capacity (up to 4200 mAh g
-1), be considered to the high-capacity cathode material of most Development volue and application potential.
But the commercial applications of silicium cathode material, still face two main bottleneck problems: i.e. own electronic poorly conductive and there is violent bulk effect (change in volume is greater than 300%) in embedding/de-lithium process of circulation.Because theoretical capacity is higher, de-/embedding along with a large amount of lithium ion in cyclic process, material volume is expansion/contraction repeatedly, causes the mechanization of material to be pulverized, and departs from gradually to lose to conduct electricity with collector substrate and be connected, and finally causes the quick decline of capacity.In addition, the change repeatedly of material volume, the solid electrolyte diaphragm that material surface also can be caused to be formed constantly destroys-lives again, and causes the lasting consumption of lithium ion, also can accelerate the attenuation process of capacity.
In order to solve the problem, improve the chemical property of silicon materials, the improvement in design on material structure and preparation technology is just extremely important.Nanometer and Composite approach improve silicium cathode material structure and the most important two kinds of methods of performance at present, plays the effect alleviated silicon materials bulk effect and improve material electronics conductivity respectively.Silicon/carbon nano-composite material combines the advantage of these two kinds of methods, is also one of system of most application prospect the while of being and studying the most deep in current silica-base material.In recent years, silicon/carbon nano-composite material has shown good electrical chemical property, but distance commercial applications still has no small distance, on the cycle performance of especially composite material, is still difficult to meet practical requirement.Therefore, set up novel method for synthesizing that is efficient and low cost, optimize silico-carbo complex method, reasonable design is carried out to the microcosmic the Nomenclature Composition and Structure of Complexes of silico-carbo composite material simultaneously, preparing the composite material having high power capacity and excellent cycling performance concurrently, is still focus and the key issue of this area research.
The early stage complex method of silicon/carbon nano-composite material, based on simple cladded type, mainly comprises that to carry out carbon to nano silicon particles or silicon nanowires (pipe) coated and at the Surface coating such as carbon nano-tube, carbon nano-fiber silicon materials.The main feature of this kind of material is that silico-carbo material tight combines, and forms the entity nanometer core/shell structure of dispersion.Because the change in volume not for silicon in structural design provides effective cushion space, carbon-coating lacking toughness and elasticity simultaneously, intensity is poor, therefore in cyclic process, be difficult to the volumetric expansion suppressing silicon, the integrality of conductive network structure can only be maintained to a certain extent with in limit cycle, very limited to the raising of cycle performance.
On this basis, people have further developed the silicon/carbon nano-composite material and embedded type silicon/carbon nano-composite material with three dimensions configuration.The former is mainly by template, first obtains regular continuous print three-dimensional silica nano-array, then it is coated to carry out carbon.The major advantage of this structure is that silicon materials have porousness and globality, the change in volume not being only silicon has reserved enough spaces, overall structure can be utilized to cushion the bulk effect of silicon simultaneously, but due to template complex process, high and the limits throughput of cost, thus still has certain difficulty in practical.Silicon nano material is mainly evenly embedded into and has in " carbon net " (or carbon skeleton) structure of three-dimension integrally configuration by embedded type silicon/carbon nano-composite material.Due to silicone content relatively low (50-60%), carbon matrix material structure accounting for main body can cushion the bulk effect embedding silicon well.From pattern, it generally can form the several microns of impalpable textures to some tens of pm, and have porous or multistage fine nanostructur, the bulk effect of silicon can be overcome from both macro and micro simultaneously, dispersion time simultaneously the globality of carbon matrix and excellent conductivity effectively can suppress the efflorescence of silicon materials machinery, the stability of maintenance electrode structure and conductive network, thus the multiplying power and the cycle performance that effectively improve composite material.From stuctures and properties, embedded type silicon/carbon nano-composite material has significant technical advantage and wide application prospect, is the emphasis of silicon/carbon nano-composite material research over the past two years.
The selection of carbon matrix material is one of key factor of the performance determining embedded type silicon/carbon nano-composite material.The kind of carbon matrix and the difference of quality, will directly cause the difference of its process based prediction model, and then the coulombic efficiency of decision composite material, high rate performance and cycle performance.Graphene is a kind of material with carbon element of excellent performance, has good conductivity, thickness is thin, intensity is high, pliability is good and chemical stability is high feature, is the ideal chose of embedded type silicon/carbon nano-composite material carbon matrix material.From structure, Graphene matrix, as coating layer, effectively can cushion and embed the bulk effect of silicon materials, the stability of maintenance electrode structure and conductive network, thus effectively improves the coulombic efficiency of composite material and multiplying power and cycle performance.In addition, Graphene volume is little, quality is light, compacted density is high, to silicon complete coated while, still can ensure that composite material has higher mass energy density and volume energy density.
In sum, embedded type silicon/graphene nanocomposite material is the system very in current embedded type silicon/carbon nano-composite material with development and application prospect.In the world, the research of embedded type silicon/graphene nanocomposite material is just at the early-stage, and its structure and synthesizing mean are all also more single, and chemical property also needs to be optimized.Be 201310265626.0 at application number, 201210520708.0,201210534860.4,201110302810.9,201110289066.3,201110247595.7,201310101854.4,201110421436.4,201010256875.X patent in, be all by silicon materials with Graphene by after simple and mechanical mixing, adopt the simple means such as suction filtration or spraying, prepare silicon-graphene composite material.And be 201110301948.7 at application number, 201110446233.0s, in the patent of 201010561749.5 and 201110289066.3, then adopt silicon dioxide or organosilicon material to mix with Graphene, and take method of reducing to prepare silicon-graphene composite material.Above-mentioned material in fact all can be regarded as a kind of mechanical impurity and non-composite material, and therefore the chemical property of this eka-silicon-grapheme material is still not ideal enough, and all unrealized practical application in full battery.
Up to the present, also do not have correlation technique to invent and can realize growth in situ graphene coated network on silicon nano material, form silicon-graphene composite structure truly, and be the full battery of high-energy-density by rational method and corresponding positive electrode assembly.In addition, on solid material, growth in situ Graphene itself is also a technical difficult problem.If this in-situ growth technology can be accomplished, for the chemical property improving silicium cathode, promote it and will have very important significance as the application of height ratio capacity lithium cell negative pole material in electric automobile and large-scale energy storage device battery system.
Summary of the invention
The object of the invention is to provide a kind of original position solid phase synthesis process and the application thereof with the spherical composite material of silicon-Graphene of multilevel hierarchy.There is the bottleneck problems such as violent bulk effect in this technology mainly in silicium cathode electron conduction difference and cyclic process, pass through technological innovation, prepare the spherical composite negative pole material of novel silicon-Graphene with excellent multiplying power and cycle performance, and be the full battery of high-energy-density with corresponding positive electrode by rational method assembly.The core of this technology selects organic carbohydrate with low cost and inorganic transition metal salt respectively as carbon source and metal catalyst precursor thing.Under high temperature heating conditions, organic carbohydrate pyrolysis forms amorphous carbon, and under the effect of the metal nano catalyst produced in position, be converted into the Graphene network configuration of high-sequential, then by the bridge linking effect of Graphene network, self assembly forms the spherical micron particles with nanometer secondary structure.The spherical composite material of silicon-Graphene prepared is prepared as high-energy-density cathode pole piece by rational method, and is the full battery system of high specific energy with the effective assembly of corresponding positive electrode.
In order to realize above object, the present invention proposes and a kind ofly one-step synthesis can have the method for the spherical composite material of silicon-Graphene of multilevel hierarchy, and being applied to lithium ion battery as high specific energy negative material.The technical solution used in the present invention is: select suitable organic carbohydrate and inorganic transition metal salt respectively as carbon source and metal catalyst precursor thing, first with silicon nano material Homogeneous phase mixing by a certain percentage.Subsequently product is placed in tube furnace, control temperature is warming up to 600-1000 DEG C, make carbon matrix precursor that in-situ heat solution occur under inertia reducing atmosphere and form amorphous carbon, metal precursor is decomposed and is reduced to the metal-catalyst nanoparticles with appropriate particle size (5-15 nm).In follow-up thermostatic process, amorphous carbon is under the catalytic action of metal-catalyst nanoparticles, and converted in-situ is the Graphene network configuration of high-sequential.Meanwhile, due to the bridge linking effect of Graphene network, the nano silicon particles of graphene coated, by being formed the spherical micron particles with meticulous nanometer secondary structure by self assembly effect, after solid phase reaction terminates, carries out removal purifying to metal nanoparticle remaining in system.The silicon prepared-spherical composite material of Graphene ball nanometer has excellent electron conduction and the feature of height ratio capacity, can when not adding conductive agent directly and negative electrode binder prepare cathode pole piece by a certain percentage.When battery complete in corresponding positive electrode assembly, cathode pole piece active material load capacity (g/cm
2) be the 10-15% of corresponding anode pole piece load capacity.
Concrete preparation method is as follows:
(1) nano silicon particles (particle diameter is between 1-1000 nm) of certain mass (0.1g ~ 100g) is first weighed; Take a certain amount of inorganic carbohydrate, control the mass ratio of carbon atom in inorganic carbohydrate and silicon materials between 1:100 to 5:100; Take certain mass transition metal inorganic salts, control the mass ratio of metal inorganic salt and silicon materials between 1:100 to 1:1000.Three's mixing is also fully ground to dispersed;
(2) be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 600-1000 DEG C, and constant temperature 1-6 h;
(3) in argon gas and hydrogen gas mixture, be cooled to room temperature, product, through pernitric acid washing 2-5 time, centrifugally obtains end product, the oven dry of 60 DEG C, vacuum;
(4) 1 ~ 10 wt% negative electrode binder and solvent are mixed together stirring, add the spherical composite material of 90 ~ 99 wt% silicon-Graphene again to stir, obtain cathode size after dispersed, finally this slurry is evenly coated on negative pole currect collecting surface, dry and obtain cathode pole piece;
(5) cathode pole piece above-mentioned steps prepared and corresponding anode pole piece, porous isolating membrane are made into naked battery core by modes such as stacked, windings, and wherein cathode pole piece active material load capacity is the 10-15% of corresponding anode pole piece load capacity.Subsequently above-mentioned naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged.Finally precharge is carried out to battery, and remove the gas in external packing, finally carry out Vacuum Package and obtain energy-density lithium ion battery.
Described organic carbohydrate comprises one or more in glucose, sucrose, ascorbic acid, polymethyl methacrylate (PMMA), polystyrene, polypropylene, naphthalenetetracarbacidic acidic acid anhydride, aromatic series and the common carbohydrates such as ring-type hydro carbons and melamine.
Described transition metal inorganic salts comprise the salt and any combination that the Common Anions used such as the cations such as nickel, iron, cobalt, manganese and sulfate radical, salt acid group, nitrate anion, acetate forms.
The arbitrary dimension of described nano silicon particles particle diameter below 1 micron, the carbon atom in solid-state carbon source and the arbitrary proportion of the mass ratio of silicon materials between 1:100 to 5:100; The arbitrary proportion of mass ratio between 1:100 to 1:1000 of metal inorganic salt and silicon materials.
Described high temperature solid state reaction temperature range is 600-1000 DEG C, and constant temperature time is 1-6 hour, and reaction atmosphere is argon gas and hydrogen mixed gas atmosphere.
Described solid phase reaction product washs 3 times through pernitric acid, and wherein nitric acid is the key component removing residual metal nano particle.
Described cathode pole piece manufacturing process, does not need additionally to add conductive agent, and the proportion of the spherical composite material of silicon-Graphene and negative electrode binder is the arbitrary proportion between 90:10 to 99:1; When assembling full battery, cathode pole piece active material load capacity is the arbitrary proportion between the 10-15% of corresponding anode pole piece load capacity.
outstanding advantages of the present invention and effect show
(1) the present invention is by a single-step solid phase reaction, and realizing nano silicon particles surface in situ growing graphene structure first, is all initiative technology at home and in the world.
(2) silicon-spherical composite material of Graphene ball nanometer of preparing of the present invention, is be made up of micron particles from pattern, but comprises meticulous nanometer secondary structure.Micron particles can from the bulk effect macroscopically overcoming inner nano silicon particles.Simultaneously in granule interior, nano silicon particles and Graphene organically combine, and are connected between nano silicon particles by Graphene, have excellent electron conduction.Gap between the meticulous nanochannel of granule interior and nano silicon particles, can play the effect of buffering silicon bulk effect further.
(3) electrochemical performance of silicon-spherical composite material of Graphene ball nanometer.This composite material can overcome silicon electron conduction difference well and there is the main technical bottleneck problem of violent bulk effect these two in embedding/de-lithium process of circulation, thus has higher reversible capacity, excellent multiplying power and cycle performance.Reversible capacity can reach 1700-1800 mAh g
-1left and right, under 1C multiplying power, can keep more than 90% of initial capacity, under 10C multiplying power, still can keep more than 75% of initial capacity.Through 200 circulations, capacity attenuation rate is less than 15%, has application prospect.When silicon-Graphene ball nano composite anode material is full battery with corresponding positive electrode assembly, cathode pole piece active material load capacity is between the 10-15% of corresponding anode pole piece load capacity, can significantly reduce negative material consumption, is beneficial to the ultralight thinning of battery.
(4) silicon-spherical composite material of Graphene ball nanometer has excellent electron conduction, when preparing cathode pole piece without the need to additionally adding conductive agent.
(5) lot stability of product is good, and synthesis technique is simple, and reappearance is splendid.
(6) preparation method's cost of the present invention is very low, and agents useful for same is cheap, is beneficial to enforcement, is very suitable for commercialization and applies.
Accompanying drawing explanation
The Technology Roadmap of the spherical composite material of solid phase fabricated in situ multilevel hierarchy silicon-Graphene in accompanying drawing 1 embodiment one.
ESEM (SEM) image of the spherical composite material of multilevel hierarchy silicon-Graphene in accompanying drawing 2 embodiment one.
Transmission electron microscope (TEM) image of the spherical composite material of multilevel hierarchy silicon-Graphene in accompanying drawing 3 embodiment one.
The long-term cycle performance of the spherical composite material of multilevel hierarchy silicon-Graphene in accompanying drawing 4 embodiment three.
The cycle performance of multilevel hierarchy silicon-graphene composite negative pole and the full battery of lithium iron phosphate positive material assembly in accompanying drawing 5 embodiment four.
Embodiment
Below in conjunction with enforcement example, the invention will be further described; what be necessary to herein means out is that following examples can only be used for further illustrating for of the present invention; can not be interpreted as content of the present invention, nonessential improvement on this basis and adjustment still belong to protection scope of the present invention.
Embodiment one
(1) first weigh the nano silicon particles (particle diameter is at 100 nm) of 10 g, weigh glucose 0.1g subsequently, ferric nitrate 0.1g, is fully ground to dispersed by three's mixture;
(2) be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 600 DEG C, constant temperature 1 hour;
(3) in argon gas and hydrogen gas mixture, be cooled to room temperature, product washs 3 times respectively through pernitric acid, centrifugally obtains end product, the oven dry of 60 DEG C, vacuum;
(4) take silicon-Graphene spherical composite material 10 g, join containing in the polyacrylic aqueous solvent of 0.1 g binding agent, mix and blend, with zirconium pearl ball milling twice, make uniform sizing material, using the Copper Foil of 9 micron thickness as collector, controlling active material load density is 0.5 g/cm
2, heat drying prepares cathode pole piece;
(5) by mass percentage, by the anode active material of phosphate iron lithium of 95%, the conductive black of 2%, the binding agent Kynoar of 3%, using n-methlpyrrolidone as solvent, mix and blend, make uniform sizing material, using the aluminium foil of 16 micron thickness as collector, above-mentioned slurry weight be coated in uniformly on aluminium foil, controlling active material load density is 5 g/cm
2, heat drying prepares anode pole piece;
(6) cathode pole piece above-mentioned steps prepared and anode pole piece and porous isolating membrane are made into naked battery core by modes such as stacked, windings.Subsequently naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged.Finally precharge is carried out to battery, and remove the gas in external packing, finally carry out Vacuum Package and obtain energy-density lithium ion battery.
Embodiment two
(1) first weigh the nano silicon particles (particle diameter is at 500 nm) of 20 g, weigh sucrose 1 g subsequently, nickel nitrate 0.2 g, is fully ground to dispersed by three's mixture;
(2) be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 800 DEG C, constant temperature 4 hours;
(3) in argon gas and hydrogen gas mixture, be cooled to room temperature, product washs 3 times respectively through pernitric acid, centrifugally obtains end product, the oven dry of 60 DEG C, vacuum;
(4) take silicon-Graphene spherical composite material 10 g, join in the aqueous solvent containing 0.5 g binding agent sodium carboxymethylcellulose, mix and blend, with zirconium pearl ball milling twice, make uniform sizing material, using the Copper Foil of 9 micron thickness as collector, controlling active material load density is 1 g/cm
2, heat drying prepares cathode pole piece;
(5) by mass percentage, by the positive active material lithium manganese phosphate of 95%, the conductive black of 2%, the binding agent Kynoar of 3%, using n-methlpyrrolidone as solvent, mix and blend, make uniform sizing material, using the aluminium foil of 16 micron thickness as collector, above-mentioned slurry weight be coated in uniformly on aluminium foil, controlling active material load density is 10 g/cm
2, heat drying prepares anode pole piece;
(6) cathode pole piece above-mentioned steps prepared and anode pole piece and porous isolating membrane are made into naked battery core by modes such as stacked, windings.Subsequently naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged.Finally precharge is carried out to battery, and remove the gas in external packing, finally carry out Vacuum Package and obtain energy-density lithium ion battery.
Embodiment three
(1) first weigh the nano silicon particles (particle diameter is at 800 nm) of 50 g, weigh polymethyl methacrylate 0.5 g subsequently, cobalt acetate 0.25 g, is fully ground to dispersed by three's mixture;
(2) be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 1000 DEG C, constant temperature 6 hours;
(3) in argon gas and hydrogen gas mixture, be cooled to room temperature, product washs 3 times respectively through pernitric acid, centrifugally obtains end product, the oven dry of 60 DEG C, vacuum;
(4) take silicon-Graphene spherical composite material 30 g, join in the aqueous solvent containing 3 g binding agent butadiene-styrene rubber, mix and blend, with zirconium pearl ball milling twice, make uniform sizing material, using the Copper Foil of 9 micron thickness as collector, controlling active material load density is 2 g/cm
2, heat drying prepares cathode pole piece;
(5) by mass percentage, by the positive active material cobalt of 95% acid lithium, the conductive black of 2%, the binding agent Kynoar of 3%, using n-methlpyrrolidone as solvent, mix and blend, make uniform sizing material, using the aluminium foil of 16 micron thickness as collector, above-mentioned slurry weight be coated in uniformly on aluminium foil, controlling active material load density is 13 g/cm
2, heat drying prepares anode pole piece;
(6) cathode pole piece above-mentioned steps prepared and anode pole piece and porous isolating membrane are made into naked battery core by modes such as stacked, windings.Subsequently naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged.Finally precharge is carried out to battery, and remove the gas in external packing, finally carry out Vacuum Package and obtain energy-density lithium ion battery.
Embodiment four
(1) first weigh the nano silicon particles (particle diameter is at 50 nm) of 100 g, weigh melamine 5 g subsequently, manganese acetate 0.5 g, is fully ground to dispersed by three's mixture;
(2) be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 900 DEG C, constant temperature 5 hours;
(3) in argon gas and hydrogen gas mixture, be cooled to room temperature, product washs 3 times respectively through pernitric acid, centrifugally obtains end product, the oven dry of 60 DEG C, vacuum;
(4) silicon-Graphene spherical composite material 50 g is taken, join in the aqueous solvent containing 4 g butadiene-styrene rubber and sodium carboxymethylcellulose hybrid adhesive (mass ratio 1:1), mix and blend, with zirconium pearl ball milling twice, make uniform sizing material, using the Copper Foil of 9 micron thickness as collector, controlling active material load density is 1.5 g/cm
2, heat drying prepares cathode pole piece;
(5) by mass percentage, by the anode active material of phosphate iron lithium of 95%, the conductive black of 2%, the binding agent Kynoar of 3%, using n-methlpyrrolidone as solvent, mix and blend, make uniform sizing material, using the aluminium foil of 16 micron thickness as collector, above-mentioned slurry weight be coated in uniformly on aluminium foil, controlling active material load density is 11 g/cm
2, heat drying prepares anode pole piece;
(6) cathode pole piece above-mentioned steps prepared and anode pole piece and porous isolating membrane are made into naked battery core by modes such as stacked, windings.Subsequently naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged.Finally precharge is carried out to battery, and remove the gas in external packing, finally carry out Vacuum Package and obtain energy-density lithium ion battery.
Claims (6)
1. there is an original position solid phase synthesis process for the spherical composite material of silicon-Graphene of multilevel hierarchy, comprise the steps:
1. select organic carbohydrate and transition metal inorganic salts respectively as carbon source and catalyst precursor; Select the nano silicon particles of particle diameter between 1-1000 nm, control the mass ratio of carbon atom in organic carbohydrate and silicon materials between 1:100 to 5:100; Three's mixing, between 1:100 to 1:1000, is also fully ground to dispersed by the mass ratio of transition metal inorganic salts and silicon materials;
2. be dispersed in crucible or porcelain boat by said mixture, and be placed in airtight tube type stove central authorities, react and carry out in argon gas and hydrogen gas mixture, control temperature rises to 600-1000 DEG C, and constant temperature 1-6 h;
3. in argon gas and hydrogen gas mixture, be cooled to room temperature, product is through pernitric acid washing 2-5 time, and centrifugal, the oven dry of 60 DEG C, vacuum, obtains end product.
2. there is the original position solid phase synthesis process of the spherical composite material of silicon-Graphene of multilevel hierarchy as claimed in claim 1, it is characterized in that organic carbohydrate in step 1 comprises in glucose, sucrose, ascorbic acid, polymethyl methacrylate (PMMA), polystyrene, polypropylene, naphthalenetetracarbacidic acidic acid anhydride, aromatic series and the common carbohydrates such as ring-type hydro carbons and melamine one or more.
3. the original position solid phase synthesis process as claimed in claim 1 with the spherical composite material of silicon-Graphene of multilevel hierarchy is characterized in that transition metal inorganic salts in step 1 comprise the salt and any combination that the Common Anions used such as the cations such as nickel, iron, cobalt, manganese and sulfate radical, salt acid group, nitrate anion, acetate forms.
4. the application of what the original position solid phase synthesis process as claimed in claim 1 with the spherical composite material of silicon-Graphene of multilevel hierarchy obtained the have spherical composite material of silicon-Graphene of multilevel hierarchy, for the negative material of lithium ion battery.
5. the assemble method with the battery of the assembling of the spherical composite material of silicon-Graphene of multilevel hierarchy utilizing the original position solid phase synthesis process with the spherical composite material of silicon-Graphene of multilevel hierarchy described in claim 1 to obtain, is characterized in that comprising the following steps:
1. taking the spherical composite material of silicon-Graphene joins in the aqueous solvent containing binding agent butadiene-styrene rubber, and mix and blend, with zirconium pearl ball milling twice, makes uniform sizing material, and using Copper Foil as collector, controlling active material load density is 2 g/cm
2, heat drying prepares cathode pole piece;
2. by the positive active material cobalt of 95% mass fraction acid lithium, the conductive black of 2% mass fraction, the binding agent Kynoar of 3% mass fraction, using n-methlpyrrolidone as solvent, mix and blend, makes uniform sizing material, using aluminium foil as collector, above-mentioned slurry weight be coated in uniformly on aluminium foil, controlling active material load density is 13 g/cm
2, heat drying prepares anode pole piece;
3. cathode pole piece above-mentioned steps prepared and anode pole piece and porous isolating membrane are made into naked battery core by modes such as stacked, windings, subsequently naked battery core is put in external packing, remove the moisture in naked battery core, quantitatively add electrolyte, leave standstill, pre-packaged, finally precharge is carried out to battery, and the gas removed in external packing, carry out Vacuum Package and obtain lithium ion battery.
6. the assemble method of what the original position solid phase synthesis process as claimed in claim 5 with the spherical composite material of silicon-Graphene of multilevel hierarchy obtained the have battery of the assembling of the spherical composite material of silicon-Graphene of multilevel hierarchy, is characterized in that cathode pole piece active material load capacity is the arbitrary proportion between the 10-15% of corresponding anode pole piece load capacity.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107768607A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN108269967A (en) * | 2016-12-30 | 2018-07-10 | 天津普兰能源科技有限公司 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene/silicon composite |
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| CN113346056A (en) * | 2021-05-17 | 2021-09-03 | 武汉科技大学 | Silicon oxide @ iron oxide/carbon composite lithium ion battery anode material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810672A (en) * | 2011-06-03 | 2012-12-05 | 株式会社半导体能源研究所 | Power storage device and method of manufacturing the same |
| CN103000377A (en) * | 2011-09-15 | 2013-03-27 | 海洋王照明科技股份有限公司 | Preparation method for negative electrode active materials and capacitors |
| CN103384001A (en) * | 2013-07-17 | 2013-11-06 | 苏州大学 | Composite graphene electrode material and solid-phase catalysis preparation method thereof |
-
2014
- 2014-03-19 CN CN201410101050.9A patent/CN104934573A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810672A (en) * | 2011-06-03 | 2012-12-05 | 株式会社半导体能源研究所 | Power storage device and method of manufacturing the same |
| CN103000377A (en) * | 2011-09-15 | 2013-03-27 | 海洋王照明科技股份有限公司 | Preparation method for negative electrode active materials and capacitors |
| CN103384001A (en) * | 2013-07-17 | 2013-11-06 | 苏州大学 | Composite graphene electrode material and solid-phase catalysis preparation method thereof |
Cited By (18)
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| CN107768607A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN107768607B (en) * | 2016-08-15 | 2020-10-16 | 福建新峰二维材料科技有限公司 | Preparation method of lithium ion battery negative electrode material |
| US10622624B2 (en) | 2016-09-19 | 2020-04-14 | Samsung Electronics Co., Ltd. | Porous silicon composite cluster and carbon composite thereof, and electrode, lithium battery, field emission device, biosensor and semiconductor device each including the same |
| CN108269967A (en) * | 2016-12-30 | 2018-07-10 | 天津普兰能源科技有限公司 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene/silicon composite |
| CN108622882B (en) * | 2017-03-18 | 2022-02-18 | 深圳格林德能源集团有限公司 | Liquid-phase codeposition preparation method of graphene |
| CN108622882A (en) * | 2017-03-18 | 2018-10-09 | 深圳格林德能源有限公司 | A kind of liquid phase co-deposition preparation method of graphene |
| CN108996494A (en) * | 2017-06-06 | 2018-12-14 | 中国科学院上海硅酸盐研究所 | A method of catalyzing and synthesizing three-dimensional grapheme |
| CN110021737A (en) * | 2018-01-09 | 2019-07-16 | 南方科技大学 | Silicon-carbon cathode material and preparation method thereof, lithium ion battery |
| CN108448080B (en) * | 2018-03-07 | 2020-12-22 | 深圳市本征方程石墨烯技术股份有限公司 | Graphene-coated silicon/metal composite negative electrode material and preparation method thereof |
| CN108448080A (en) * | 2018-03-07 | 2018-08-24 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof |
| CN109755515B (en) * | 2018-12-27 | 2020-05-22 | 信阳师范学院 | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof |
| CN109755515A (en) * | 2018-12-27 | 2019-05-14 | 信阳师范学院 | A kind of lithium ion battery silicon/anode composite and preparation method thereof |
| CN109659549A (en) * | 2019-01-14 | 2019-04-19 | 北京科技大学 | Lithium battery multilevel structure silicon-porous carbon compound cathode materials preparation method |
| CN110148736A (en) * | 2019-06-03 | 2019-08-20 | 哈尔滨工业大学 | A kind of silicon/carbon nanotube/cobalt composite material preparation method and applications |
| CN114497552A (en) * | 2020-10-28 | 2022-05-13 | 南京大学 | Preparation method and application of silica graphene framework composite material |
| CN113346056A (en) * | 2021-05-17 | 2021-09-03 | 武汉科技大学 | Silicon oxide @ iron oxide/carbon composite lithium ion battery anode material and preparation method thereof |
| CN117463999A (en) * | 2023-12-28 | 2024-01-30 | 天津大学 | Copper-based conductive composite material and preparation method and application thereof |
| CN117463999B (en) * | 2023-12-28 | 2024-03-22 | 天津大学 | Copper-based conductive composite material and preparation method and application thereof |
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